Vat dyestuffs of the acedianthrone series



United States Patent OF THE ACEDIANTHRO SERIES Armin Caliezi, Basel, andWalter Kern, Sissach, Switzep land, assignors to Ciba Limited, Basel,Switzerland No Drawing. Filed Sept. 30, 1957, Ser. No. 686,829

Claims priority, application Switzerland May 26, 1954 5 Claims. (Cl.260-351) VAT DYESTUFFS This application is a continuation-in-part ofcopending aPPlication Serial No. 510,532 filed May 23, 1955 (Patent .No.2,827,464, granted March 18, 1958).

This invention relates to vat dyestuffs of the acedis anthrone seriesand to a process for their manufacture.

According to the invention valuable vat dyestuffs of the acedianthroneseries are obtained when approximately 1 mol of a dihalogenanthraqujnone is reacted with 2 mols of a mono-amino-acedianthrone or 1mol of a monoamino-acedianthrone and 1 mol of anotheramino-anthraquinone. For example 1:5-, 2:6- or 2:7- dichloroor -dibromanthraquinone or 6-Bz-l-dibromobenzanthrone,

have proved to be suitable dihalogen anthr'aquinone compounds for useaccording to this invention.

In the process of the invention 1 mol of such a dihalogen anthraquinonecompound is reacted either with 2 mols of a mono-amino-acedianthrone or1 mol of a mono-'amino acedianthrone and 1 mol of anotheraminoanthraquinone. As suitable aminoanthraquinones there may bementioned 1- or Z-aminoanthraquinone and 1- amino-4- or-S-benzoylaminoanthraquinone.

The mono-amino-acedianthrones to be used as starting materials can beobtained by mononitration of acedianthrone of the formula IH I l inwhich Ac indicates an acedianthroneradical in which the NH-groupoccupies the same position as the nitro group in thenitro-acedianthrone, Aq stands for an anthraquinone radical and Aq' is'aradical of an anthraquinone compound, preferably an acedianthroneradical.

2,945,866 Patented July 19, 1960 1 ice These products constitutevaluable brown vat dyestufis which can be used for the dyeing of a widevariety of materials, more especially natural and regenerated cellulose.They can also be used as pigments. These dyestufi's are particularlysuitable for printing and give brown prints in which there is no damageto the fiber and the colors are strong.

The following examples illustrate the invention, the parts andpercentages being by weight unless otherwise stated and the relation ofpart by weight to part by volume being the same as that of the kilogramto the liter.

Example 1 2.77 parts of 2:7-dichloranthraquinone, 8.4 parts ofamino-acedianthrone, 1 part of copper powder, 1.5 parts of sodiumcarbonate and 100 parts of nitrobenzene are heated for 17 hours toZOO-220 C. The mixture is then allowed to cool to 100 C. and theprecipitated dyestufi filtered off. It is washed with nitrobenzene andalcohol and then extracted by boiling with dilute hydrochloric acid.After drying, 9.2 parts of a brown powder are obtained which dyes andprints cotton a very strong reddish brown. The dyestuif has the formulaAcedianthrone zrNH-rv -NH-Aeedianthrone using, instead of2:7-dichloranthraquinone, 2:6! dichloranthraquinone, a dyestulf of theformula NH-Acedianthrone Acedlanthrone-NH-- having similar propertiesispbtained.

Example 2 60 parts of nitrobenzene, 3.3 parts of2:7-dichloranthraquinone. 5 parts of amino-acedianthrone, 2.7 partsof 1-amino-anth raquinone, 0.6 part ,of copper powder and 2.7 parts of sodiumcarbonate are heated for 20 hours to 2l0-220 C. and then worked up as inExample 1, 8.5 parts are obtained of a brown powder which dyes andprints cotton in fast red brown shades. The dyestufli has the formulaAcedianthroneHN.

Example 3 parts of naphthalene, 6 parts of amino-acedianthrone, 2.7parts of 6-Bz-l-dibromobenzanthrone,0.5 part vof cuprous chloride, 0.5part of copper powder and 1 part of sodium carbonate are heated underreflux for 20 hours. The mixture is then allowed to cool to C., 100parts of chlorobenzene added and the precipitated dyestulf filtered offat 80 C. After working up as de- 1 scribed in Example 1, a black brownpowder is obtained '3 which dyes and prints cotton in strong red brownshades. The dyestutf has the formula fiNH-AWdianthront:

Acedianthrona Example 4 100 parts of nitrobenzene, 8.2 parts ofamino-acedianthrone, 2.8 parts of 1:S-dichloranthraquinone, 1 part ofcopper powder and 1.5 parts of sodium carbonate are heated for- 17 hoursto 210-220 C. and then worked up as described in Example 1. A dyestuffhaving the is obtained which dyes and prints cotton in fast, yellowishbrown shades.

Example 5 1 part of the dyestuff prepared according to Example 4 isstirred in 10 parts of chlorsulfonic acid for 20 hours at 20. C. Thesolution is then poured on ice and water and the precipitated dyestuifisolated. It dyes cotton from the vat in strong, fast red brown shades.

Example 6 Into a melt of 40 parts of aluminum chloride and 8 parts ofsodium chloride are introduced at 120 C., 2. parts of the dyestuffprepared according to Example 4. After the melt has been stirred for 1hour at 120 C., it is poured on ice and water. .By-the addition ofhydrochloric acid the aqueous mixture is rendered acid and it is thenheated for A hour to 8.0 C. and the dyestufl filtered off. It dyescotton in a fast brown of strong color. V V Example 7 I 1 part of thedyestuif obtained according to Example 1 is vatted in 100 parts of waterwith the addition of 4 .parts by volume of sodium hydroxide solutionwith 2 parts of sodium hydrosulphite at 45 C. The resulting stock vat isadded'to a solution of 4 parts-by volume of 30% sodium hydroxidesolution and 2 parts of sodium hydrosulphite in 2,000 parts of water. Inthe resulting dye bath 100 parts of cotton are dyed for 1 hour at 40- 50C. with the addition of 10 parts of sodium chloride. The cotton is thensqueezed out, oxidized in the air, rinsed and soaped at the boil. It isdyed in strong reddish brown shades of good fastness properties.

Example 8 200 parts of the dyestulf obtained according to Example 1, ina finely divided form, are mixed to a paste with 100 parts of water, 600parts of a potash thickening (prepared from 90 parts of wheat starch,330 parts of water, 100 parts of glycerol, 140 parts of British gum,.170 parts of tragacanth mucilage and 170 parts of potassium carbonate)and 100 parts of hydrosulphite. A cotton fabric is printed with thispaste. After printing, the fabric is driedwith moderate heat and thensteamed at 101-103 C. for 5-10 minutes in air-free, wet steam, rinsed inrunning water until the dyestuff is re-oxidized and soaped at the boil.A strong, fast red brown print is gbtained.

What is claimed is:

1. A vat dyestnif of the formula in which Ac indicates an acedianthroneradical in which the --NH-group occupies the same position as the nitrogroup in the mononitro-acedianthrone obtained by mononitration ofacedianthrone and reduction of the'resulting nitro compound, and Aqstands for a member selected from the group consisting of theanthraquinonyl and benzanthronyl radicals.

2. The vat dyestufi of the formula Acedianthrone-NH NH-Aeedianthronewherein the --NH-group occupies the same position on its adjacentacedianthrone radical as does the nitro group on themononitro-acedianthrone obtained by mononitration of acedianthrone andreduction of the resulting nitro compound.

3. The vat dyestulf of the formula NH-Acedianthrone Ac edianthrone-NHwherein the NH -group occupies the same position on its adjacentacedianthrone radical as does the nitro group on themononitro-acedianthrone obtained'by mononitration of acedianthrone andreduction of the resulting nitro compound.

4. The vat dyestuff of the formula (H) I|-IHAcedianthrone NH OAcedianthrone 1 wherein the NH-group occupies the same position on itsadjacent acedianthrone radical as does the nitro group on themononitro-acedianthrone obtained by mononitration of acedianthrone andreduction of the resulting nitro compound.

5. The vat dyestuif of the formula NH-A cedianthrono References Cited inthe file of this patent v UNITED STATES PATENTS 2,827,644 Caliezi et a1.Mar. 18, 1958 FOREIGN PATENTS I 672,906 GreatBritain May 28., 1952

1. A VAT DYESTUFF OF THE FORMULA